CN105689734B - A kind of method of Cu contents in accurate control Cu doping Pt hollow nano-materials - Google Patents

A kind of method of Cu contents in accurate control Cu doping Pt hollow nano-materials Download PDF

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CN105689734B
CN105689734B CN201610071500.3A CN201610071500A CN105689734B CN 105689734 B CN105689734 B CN 105689734B CN 201610071500 A CN201610071500 A CN 201610071500A CN 105689734 B CN105689734 B CN 105689734B
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doping
hollow nano
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contents
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CN105689734A (en
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田亮亮
夏楷东
杨聪
陈艳玲
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Chongqing University of Arts and Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0549—Hollow particles, including tubes and shells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like

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Abstract

The invention discloses a kind of method of Cu contents in accurate control Cu doping Pt hollow nano-materials, comprise the following steps：（1）By Cu2O is dispersed in water, is added under 20 25 DEG C of stirring conditions and is contained PtCl6 2‑The aqueous solution, the PtCl of addition6 2‑With Cu2O mol ratio is 1.5 2.5:1, the pH value of regulation system is 4.5 5.5；（2）System is heated to 60 DEG C with 1 DEG C/min heating rate, 10 180min are reacted at this temperature；（3）Cu is removed after the completion of reaction2O cores, obtain the Pt hollow nano-materials of Cu doping.The present invention is by controlling the key parameters such as raw material proportioning, pH value, heating condition, reaction time in preparation process, to realize the control of Cu contents in the Pt hollow nano-materials adulterated to Cu, so as to control and adjust its catalytic performance.

Description

A kind of method of Cu contents in accurate control Cu doping Pt hollow nano-materials
Technical field
The present invention relates to hollow nano-material technical field, and in particular to a kind of accuracy control method of Cu doping contents.
Background technology
Platinum is hollow nanostructured to have big specific surface area and abundant pore structure, small component units, Neng Gourong Receive substantial amounts of guest molecule or larger-size molecule, make it have excellent electro catalytic activity, make it in biochemistry, catalysis The fields such as, material science have special application prospect.But the hollow nanostructured surface nature of single platinum is single, urging Substantial amounts of intermediate product is easily adsorbed during change, catalyst poisoning is caused, its electro catalytic activity is greatly reduced.To single platinum Hollow nano-material, which carries out Copper-cladding Aluminum Bar, can regulate and control its surface charge distribution in catalytic process, promote the regeneration of catalytic site position, Its catalytic activity and anti-poisoning ability are improved while platinum consumption is reduced, is a kind of not only economical but also effectively method.
Cu2O/Cu oxidation-reduction pair values (- 0.36V) are than precious metals pt Cl6 2-/ Pt (0.735V) is much lower, therefore Cu2O can be with PtCl6 2-Occur spontaneous oxidation reduction reaction to reach in its Surface coating Pt purpose, finally remove Cu2O Template obtains being based on Cu2The Pt of O patterns is hollow nanostructured.Due to Cu under acid condition+Disproportionated reaction, platinum can produced Elemental copper is produced simultaneously, so as to form the Pt hollow nano-materials of Cu doping.
For the Pt hollow nano-materials that Cu adulterates, its composition is the influence most important factor of its catalytic activity.Mesh It is preceding to think that the simple substance Cu produced is side reaction product the research in the field more, it can not accurately control formed Cu to adulterate Pt The composition of hollow nano-material, therefore also can not just realize the control to its catalytic activity.Finding one kind accurately can control Cu to mix The method of miscellaneous Pt hollow nano-material compositions is just particularly important.
The content of the invention
In view of this, it is an object of the invention to provide Cu contents in a kind of accurate control Cu doping Pt hollow nano-materials Method, so as to realize the control to its catalytic activity.
To reach above-mentioned purpose, the present invention provides following technical scheme：
The method of Cu contents, comprises the following steps in a kind of accurate control Cu doping Pt hollow nano-materials：
(1) by Cu2O is dispersed in water, is added under 20-25 DEG C of stirring condition and is contained PtCl6 2-The aqueous solution, plus The PtCl entered6 2-With Cu2O mol ratio is 1.5-2.5: 1, and the pH value of regulation system is 4.5-5.5；
(2) system of step (1) is heated to 60 DEG C with 1 DEG C/min heating rate, 10- is reacted at this temperature 180min；
(3) Cu is removed after the completion of reacting2O cores, obtain the Pt hollow nano-materials of Cu doping.
Further, the Cu2O is the Cu of cubic structure2O。
Further, the Cu of the cubic structure2O is prepared by following methods：Under 50-60 DEG C of stirring condition, toward CuCl2It is molten Excessive NaOH solution reaction 0.5-1h is added in liquid, is centrifuged after ascorbic acid solution, reaction 3-4h are then added dropwise again, then distinguish Cleaned, be finally dried in vacuo with water and ethanol, obtain the Cu of cubic structure2O。
Further, in the step (1), PtCl is contained6 2-The aqueous solution be H2PtCl6The aqueous solution.
Further, in the step (3), product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction, The ammoniacal liquor complexing for adding 18%-25% removes Cu2O cores, obtain the Pt hollow nano-materials of Cu doping.
The beneficial effects of the present invention are：
The present invention by controlling the key parameters such as raw material proportioning, pH value, heating condition, reaction time in preparation process, To realize the control of Cu contents in the Pt hollow nano-materials adulterated to Cu, so as to control and adjust its catalytic performance.
Embodiment
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, below by the preferred reality of the present invention Example is applied to be described in detail.
According to Cu2The diversity of O patterns and size, can design and synthesize the Pt hollow Nanos of the Cu doping of different structure Material, following examples are with the Cu of cubic structure2Exemplified by O.
The Cu for the cubic structure that following examples are used2O is prepared by following methods：
Under 55 DEG C of stirring conditions, to the CuCl that 100ml concentration is 0.01mol/L210mL concentration is added in solution is After 2mol/L NaOH solution, reaction 0.5h, then the ascorbic acid solution that 10ml concentration is 0.6mol/L is slowly added dropwise, instead Answer after 3h, centrifuge, cleaned respectively with water and ethanol, last 40 DEG C of vacuum drying 12h obtains the Cu of cubic structure2O。
Embodiment 1
The preparation method of the Pt hollow nano-materials of the Cu doping of embodiment 1, comprises the following steps：
(1) by Cu2O is dispersed in water, and H is added under 20 DEG C of stirring conditions2PtCl6The aqueous solution, the H of addition2PtCl6 With Cu2O mol ratio is 2.5: 1, and the pH value of regulation system is 4.5；
(2) system of step (1) is heated to 60 DEG C with 1 DEG C/min heating rate, 20min is reacted at this temperature；
(3) product is centrifuged into 5min under the conditions of 5000 turns after the completion of reacting, the ammoniacal liquor complexing for adding 20% removes Cu2O Core, obtains the Pt hollow nano-materials of Cu doping.
After testing, Cu weight content is 24.8% in the Pt hollow nano-materials for the Cu doping that prepared by embodiment 1.
Embodiment 2
The preparation method of the Pt hollow nano-materials of the Cu doping of embodiment 2, comprises the following steps：
(1) by Cu2O is dispersed in water, and H is added under 20 DEG C of stirring conditions2PtCl6The aqueous solution, the H of addition2PtCl6 With Cu2O mol ratio is 2.0: 1, and the pH value of regulation system is 5.0；
(2) system of step (1) is heated to 60 DEG C with 1 DEG C/min heating rate, 60min is reacted at this temperature；
(3) product is centrifuged into 5min under the conditions of 8000 turns after the completion of reacting, the ammoniacal liquor complexing for adding 20% removes Cu2O Core, obtains the Pt hollow nano-materials of Cu doping.
After testing, Cu weight content is 51.1% in the Pt hollow nano-materials for the Cu doping that prepared by embodiment 2.
Embodiment 3
The preparation method of the Pt hollow nano-materials of the Cu doping of embodiment 3, comprises the following steps：
(1) by Cu2O is dispersed in water, and H is added under 25 DEG C of stirring conditions2PtCl6The aqueous solution, the H of addition2PtCl6 With Cu2O mol ratio is 1.5: 1, and the pH value of regulation system is 5.5；
(2) system of step (1) is heated to 60 DEG C with 1 DEG C/min heating rate, 120min is reacted at this temperature；
(3) product is centrifuged into 5min under the conditions of 8000 turns after the completion of reacting, the ammoniacal liquor complexing for adding 25% removes Cu2O Core, obtains the Pt hollow nano-materials of Cu doping.
After testing, Cu weight content is 73.6% in the Pt hollow nano-materials for the Cu doping that prepared by embodiment 3.
The present invention by controlling the key parameters such as raw material proportioning, pH value, heating condition, reaction time in preparation process, To realize the control of Cu contents in the Pt hollow nano-materials adulterated to Cu, so as to control and adjust its catalytic performance.Following table is lifted Example lists the Pt hollow nano-material products of the Cu doping of three kinds of difference Cu content ranges by controlling above-mentioned parameter to obtain.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (5)

1. a kind of method of Cu contents in accurate control Cu doping Pt hollow nano-materials, it is characterised in that：Comprise the following steps：
（1）By Cu2O is dispersed in water, is added under 20-25 DEG C of stirring condition and is contained PtCl6 2-The aqueous solution, regulation system PH value；
（2）By step（1）System be heated to 60 DEG C with 1 DEG C/min heating rate, certain time is reacted at this temperature；
（3）Cu is removed after the completion of reaction2O cores, obtain the Pt hollow nano-materials of Cu doping；
Following reaction condition is controlled to realize that the Cu contents of the Pt hollow nano-materials of Cu doping are accurately controlled by above step：
H2PtCl6With Cu2O mol ratio PH value Heating condition Reaction time Cu weight content in product 2.5:1 4.5 1 DEG C/min is heated to 60 DEG C 10-30min 20%-30% 2.0:1 5.0 1 DEG C/min is heated to 60 DEG C 30-90min 45%-55% 1.5:1 5.5 1 DEG C/min is heated to 60 DEG C 90-180min 70%-80%
。
2. the method for Cu contents in accurate control Cu doping Pt hollow nano-materials according to claim 1, its feature exists In：The Cu2O is the Cu of cubic structure2O。
3. the method for Cu contents in accurate control Cu doping Pt hollow nano-materials according to claim 2, its feature exists In：The Cu of the cubic structure2O is prepared by following methods：Under 50-60 DEG C of stirring condition, toward CuCl2Added in solution excessive NaOH solution reaction 0.5-1h, be then added dropwise ascorbic acid solution again, centrifuged after reaction 3-4h, then clear with water and ethanol respectively Wash, be finally dried in vacuo, obtain the Cu of cubic structure2O。
4. the method for Cu contents in accurate control Cu doping Pt hollow nano-materials according to claim 1, its feature exists In：The step（1）In, contain PtCl6 2-The aqueous solution be H2PtCl6The aqueous solution.
5. the method for Cu contents in accurate control Cu doping Pt hollow nano-materials according to claim 1, its feature exists In：The step（3）In, product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction, adds 18%-25%'s Ammoniacal liquor complexing removes Cu2O cores, obtain the Pt hollow nano-materials of Cu doping.
CN201610071500.3A 2016-02-02 2016-02-02 A kind of method of Cu contents in accurate control Cu doping Pt hollow nano-materials Active CN105689734B (en)

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DE3161354D1 (en) * 1980-03-24 1983-12-15 Ytkemiska Inst A liquid suspension of particles of a metal belonging to the platinum group, and a method for the manufacture of such a suspension
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Inventor after: Tian Liangliang

Inventor after: Wu Shenping

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Inventor before: Xia Kaidong

Inventor before: Yang Cong

Inventor before: Chen Yanling